CN105056902B - Method for treatment of anionic pollutant containing wastewater with modified tobacco straw - Google Patents
Method for treatment of anionic pollutant containing wastewater with modified tobacco straw Download PDFInfo
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Abstract
Belonging to the technical field of water treatment in water pollution control, the invention specifically relates to a method for treatment of anionic pollutant containing wastewater with modified tobacco straw. The method includes: employing organic-inorganic cationic monomer graft copolymerization to perform straw fiber modification, firstly pretreating tobacco straw with a sodium hydroxide solution to separate straw cellulose, then under an N2 protection environment, using ceric ammonium nitrate as the initiator, subjecting the pretreated tobacco straw and dimethyl diallyl ammonium chloride, aluminum sulfate to graft copolymerization reaction so as to prepare a straw modified material, then using the modified material to remove organic anionic pollutants and inorganic anionic pollutants from water respectively, thus finally realizing treatment of anionic pollutants in wastewater.
Description
Technical field
The invention belongs to the water-treatment technology field in water prevention and cure of pollution, more particularly to containing the place of anionic pollutant waste water
Reason, it is specially a kind of to process the method containing anionic pollutant waste water using modified tabacco straw.
Background technology
In recent years, with the volume increase of grain, straw quantity is significantly increased, the t of China agricultural crop straw annual production about 700,000,000
Mark coal.Meanwhile, with the continuous adjustment of Industry Structure, stalk is greatly reduced used in life, causes a large amount of agricultural straw
Stalk is remaining and burned or abandoned everywhere by field.By taking tabacco straw as an example, national cigarette district about produces every year tabacco straw 4500kt,
Overall utilization is very low, most by open incineration, not only waste of resource but also atmosphere pollution.At present, the overall utilization of China's stalk
Only 33%, wherein only accounting for 2.6% or so through technical finesse.Therefore, new technology is developed, improves the comprehensive profit of agricultural stalk
With rate, turn waste into wealth, be of great immediate significance to improving resource scarcity problem and preserving the ecological environment.
It is agricultural crop straw abundance, cheap, biodegradable, not only containing plant growth needed for various nutrition
Composition, simultaneously containing abundant organic matter, so as to determine that straw has huge potential using value.Stalk has in itself
The advantages of porous, specific surface area are big, proportion is little, with certain compatibility, but adsorption capacity is not strong, main group of stalk
Contain various hydroxyls, carboxyl isoreactivity functional group on portion of cellulose and lignin, the chemistry such as can be etherified, be esterified to it
It is modified, introduce corresponding effect group.Therefore, stalk is modified and paractical research is gradually by the pro-gaze of scholars.
Wherein, it is a big heat of current utilization of waste as resource and waste water treatment research field in wastewater treatment by stalk modification application
Point.At present, the stalk application in terms of water process that is modified is concentrated mainly on the following aspects：(1) novel flocculant；(2) work(
Can adsorbent；(3) ion-exchanger.
However, the physicochemical property for determining modified straw application function is but regulated and controled by raw material and modified condition etc..First, it is just former
For material, including stalk species and modifying agent.The agricultural stalk resource of wide material sources is different in component and properties, generally
Woody material content of lignin is higher；And gramineae plant cellulose and hemicellulose level are higher, hole is higher.Additionally, modified
Product is different and widely different because modifying agent, and the modified product that general cation modifier is produced has cationic characteristic, cloudy
Ion modification agent product has anionic nature.Secondly, when modified condition mainly includes reactant ratio, reaction temperature and reaction
Between.Modified straw each several part active principle prepared by different ratios of raw materials differs greatly, thus its physicochemical property is also not quite similar.
The temperature sensitive point and heat endurance of stalk each component and reaction raw materials differs, and generally, each source chemicals reaction under low temperature is lived
Property is not strong enough, and modified-reaction is not abundant enough；The too high destruction for being likely to cause some functional groups of temperature causes side reaction.Cause
This, control a suitable temperature range to modified-reaction carry out in order it is extremely important.Reaction time mainly affects modified anti-
The degree answered, the time is too short, and modified-reaction not exclusively cannot obtain effective product；Overlong time not only waste of materials and when
Between, while being likely to cause the carrying out of side reaction and reduce yield.Thus the rational reaction time is controlled to modified product
Physicochemical property is significant.In a word, cause the factor of stalk modified product nature difference a lot, the modified of agricultural stalk should
The carrying out that should be shot the arrow at the target, should further develop according to specific demand.
With developing rapidly for industry, waste water pollution problem is increasingly serious, and water pollutant species also becomes increasingly complex, hardly possible
Degraded.Anion and the class of cationic pollutant two can be classified as from pollutant electronegativity, wherein anionic pollutant divides again
For organic anion pollutant and inorganic anion pollutant；Cationic pollutant is divided into organic cation pollutant and inorganic sun
Ionic contamination.The processing method of different types of pollutant is not quite similar with principle, at present, using at most, technology maturation and
Cheap is absorption method.Research to adsorbent even more emerges in an endless stream, but divides wastewater property and research and develop exclusive adsorbent
Research is but more rare.Therefore, for characteristic contamination, the exclusive adsorbent for developing highly effective is current water technology
Key.
In sum, with Discarded Tobacco stalk as raw material, cationic adsorption agent is prepared, is mainly used in anion in water
The research of the exclusive absorption of pollutant is significant in terms of utilization of waste as resource and waste water treatment.
The content of the invention
The purpose of the present invention be Discarded Tobacco stalk is carried out it is cation-modified, by the suction to different anions in waste water
Attached removing is processed, and reaches resource reutilization.The present invention has raw material sources extensively, and process is simple is easy to control, product adsorption effect
The advantages of good.
To achieve these goals, the technical scheme of employing is as follows：
It is a kind of to process the method containing anionic pollutant waste water using modified tabacco straw, first with sodium hydroxide solution pair
Tabacco straw carries out pretreatment and isolates stalk cellulose, then in N2Under environmental protection, with ammonium ceric nitrate as initiator, will be pre-
Process tabacco straw carries out graft copolymerization with dimethyl diallyl ammonium chloride (DADMAC) and aluminum sulfate, prepares stalk and changes
Property material, recycle this material modified dirty to organic anion pollutant (congo red) in water body and inorganic anion respectively
Dye thing (P-PO4 3-) removal, it is final to realize the process containing anionic pollutant waste water.Pre-treat tobacco stalk and DADMAC
(60% aqueous solution) and Al2(SO4)3Respectively to add than as 1g/4mL and 1g/2g carries out hybrid reaction.Described NaOH
Weight/mass percentage composition be 10%.
Tabacco straw is mainly made up of cellulose, hemicellulose, lignin, by crushing, alkali profit the pretreatment such as rise, no
Only can dissolve hemicellulose, lignin, impurity etc., the form and fine structure that can also make stalk cellulose changes,
So as to improve the reactivity worth of cellulose, and three alcoholic extract hydroxyl groups are respectively provided with stalk cellulose each basic ring, these activity hydroxies
Allow cellulose that chemical reaction to occur with other activated monomers, by pretreated stalk and inorganic-organic cationic monomer
Composite polymeric reacts, and the product for obtaining can be used for the process containing anionic pollutant waste water.
Modified straw raw materials are tabacco straw, and its component analysis and Industrial Analysis are shown in Table 1.
The tabacco straw component analysis of table 1 and Industrial Analysis
Using different types of anionic pollutant in modified tabacco straw processing solution, organic anion pollutant is with firm
Annotto simulated wastewater be representative, the P-PO that inorganic anion pollutant is prepared with potassium dihydrogen phosphate4 3-Simulated wastewater is generation
Table.
Distinguish the P- that the congo red waste water and concentration that concentration for the treatment of is 100mg/L is 20mg/L using modified straw
PO4 3-(in terms of P) simulated wastewater.It is 25mL in waste water taken amount, when reaction temperature is 20 DEG C (room temperature), modified straw dosage is
It is that modified straw is to Congo red in 2min～48h condition and ranges in 3～11, reaction time that 0.002～0.050g, wastewater pH are
Highest clearance can reach more than 99%, and adsorbance is up to 230mg/g；When modified straw dosage be 0.002～0.200g,
It is that modified straw is to P-PO in 2min～48h condition and ranges in 3～11, reaction time that wastewater pH is4 3-Highest clearance it is reachable
More than 70%, adsorbance is up to 18mg/g.Wherein, under 0.01g modified straw dosages, Congo red absorption is reached in 4h
To apparent equilibrium, the absorption to P basically reaches apparent equilibrium in 36h.
Congo red and P-PO is carried out respectively to modified straw at a temperature of 20 DEG C4 3-The isothermal adsorption test of waste water, wherein,
Congo red concentration range is：10～1000mg/L；P-PO4 3-Concentration range is：1～1000mg/L.Using Langmuir and
Freundlich Isothermal Models are fitted to result of the test, find correlation of two models to Congo red and P absorption fittings
Coefficient (R2) it is all higher than 0.9, and the R of Langmuir2R more than Freundlich2, illustrate two kinds of models for modified straw pair
Congo red and P absorption in water body all has preferable fitting effect, and absorption of the modified straw to two kinds of pollutants more meets
Langmuir adsorption isotherms, show that modified straw is between single or multiple lift absorption, and to change to Congo red and P absorption
The absorption surface of property stalk has inhomogeneities.N values obtained by Freundlich models fittings are all higher than 1, illustrate modified straw
It is higher to Congo red and P adsorption strength, with stable adsorption effect.
Stalk pretreatment is concretely comprised the following steps：The tabacco straw of the mesh sieve of a certain amount of mistake 60 is weighed in reactor, according to liquid
Material is than being 15:1(mL:G) H that a certain amount of mass concentration is 10% NaOH and mass concentration is 3% is added2O2(wherein NaOH with
H2O2Volume ratio is 5:1), it is uniformly mixed, 50 DEG C of immersion 4～5h of activation in thermostat water bath.Then suction filtration, with distillation
Water cleaning is until neutral, 65 DEG C of drying, standby.
Stalk is modified to be concretely comprised the following steps：Stalk 5g after pretreatment is weighed in 250mL triangular flasks, plus 80mL distilled water
Infiltration, is subsequently adding Al2(SO4)3And DADMAC, stir and evenly mix, catalysis initiator ammonium ceric nitrate is added, stir evenly.Logical nitrogen is about
10min, and it is maintained at N2Under environment, regulating and controlling temperature, reaction a period of time.1～2h is stored at room temperature, successively with ethanol and distilled water
Washes clean, 65 DEG C of drying, obtains final product tabacco straw material modified (being named as AD-MTS).Regulate and control modified condition respectively：Pretreatment
Stalk (TS):DADMAC (g/ml) is 1:4～4:1st, pretreated straw：Al2(SO4)3(g/g) it is 1:4～4:1st, reaction temperature is
20～100 DEG C, the reaction time be 1～5h, pretreated straw：Ammonium ceric nitrate (g/g) is 1:1～10:1, it is modified condition excellent
Change, show that optimal modifying technology conditions are：TS：DADMAC (g/mL) is 1：2, TS：Al2(SO4)3(g/g) it is 1：2, reaction temperature
60 DEG C, the time be 2h, TS：Ammonium ceric nitrate ratio (g/g) is 6：1.
Modified straw practical application：By the modified straw produced be added separately to 100mg/L congo red waste water and
The P-PO of 20mg/L4 3-In waste water, while it is that 3～11, modified straw dosage is 0.002～0.200g, reaction to adjust wastewater pH
Time is 2min～48h, and modified straw can reach more than 99% to Congo red highest clearance, and adsorbance is up to 230mg/
g；Modified straw is to P-PO4 3-Highest clearance up to more than 70%, adsorbance is up to 18mg/g.Wherein, it is modified in 0.01g
Under stalk dosage, apparent equilibrium is reached in 4h to Congo red absorption, the absorption to P basically reaches apparent equilibrium in 36h.
The positive effect of the present invention is：
(1) the technical program have good adsorption effect, adsorbing and removing anionic pollutant ability it is strong, easy to use,
It is cost-effective；
(2) recycling of agricultural stalk is not only solved, while can also realize to waste water containing anionic pollutant
Purified treatment.
Description of the drawings
Fig. 1 is the red of the modified straw of stalk, modified straw, the modified straw for adsorbing Congo red saturation and absorption P saturations
External spectrum figure.
Fig. 2 is stalk scanning electron microscope (SEM) photograph.
Fig. 3 is modified straw scanning electron microscope (SEM) photograph.
Fig. 4 is the modified straw scanning electron microscope (SEM) photograph for adsorbing Congo red saturation
Fig. 5 is the modified straw scanning electron microscope (SEM) photograph for adsorbing P saturations
Fig. 6 is stalk Zata potential diagrams
Fig. 7 is modified straw Zata potential diagrams
Specific embodiment
Below in conjunction with instantiation, explanation is explained in detail to the present invention.
Embodiment 1：
1st, the preparation of modified straw
(1) tabacco straw pretreatment
Tabacco straw surface dirt is cleaned with running water, is placed in 80 DEG C of drying in baking oven, be cut into segment, the powder of 3～5cm
Broken, 60 mesh sieves excessively.It is 15 according to liquid ratio:1(mL:G) add 20.0g stalks, the NaOH that 250mL mass concentrations are 10%,
50mL mass concentrations are 3% H2O2In 500ml beakers, be uniformly mixed, in thermostat water bath 50 DEG C immersion activation 4～
5h.Then suction filtration, is cleaned until neutral with distilled water, and 65 DEG C dry to constant weight, standby.
(2) tabacco straw is modified
1. weigh the pretreated stalk 5g of Jing (1) successively to steam in the 250mL triangular flasks of several different labels, plus 80mL
Distilled water infiltrates, and is subsequently adding 5g Al2(SO4)3, stirring and dissolving is mixed, then measures DADMAC20mL, 10mL, 5mL, 2.5mL respectively
It is added in the triangular flask of different labels with 1.25mL, then adds initiator ammonium ceric nitrate 0.833g, stirs.Logical nitrogen is about
10min, and it is maintained at N2Under environment, bath temperature is placed in for 80 DEG C, mixing speed in the water-bath of 400r/min to react 2h
Afterwards, 1～2h being stood at room temperature, then with ethanol and distilled water product being washed respectively, 65 DEG C dry to constant weight.
2. weigh the pretreated stalk 5g of Jing (1) successively to steam in the 250mL triangular flasks of several different labels, plus 80mL
Distilled water infiltrates, and Al is weighed respectively2(SO4)320g, 10g, 5g, 2.5g and 1.25g are added in the triangular flask of different labels, then
Addition 2.5mLDADMAC, stirs and evenly mixs, then adds initiator ammonium ceric nitrate 0.833g, stirs.Logical nitrogen about 10min, and
It is maintained at N2Under environment, bath temperature is placed in for 80 DEG C, after mixing speed is for reaction 2h in the water-bath of 400r/min, in room temperature
1～2h of lower standing, is then washed with ethanol and distilled water respectively to product, and 65 DEG C dry to constant weight.
3. weigh the pretreated stalk 5g of Jing (1) successively to steam in the 250mL triangular flasks of several different labels, plus 80mL
Distilled water infiltrates, and sequentially adds 5g Al2(SO4)3And 2.5mLDADMAC, stir and evenly mix, then add initiator ammonium ceric nitrate
0.833g, stirs.Logical nitrogen about 10min, and it is maintained at N2Under environment, respectively regulate and control bath temperature be 20 DEG C, 40 DEG C, 60
DEG C, 80 DEG C and 100 DEG C, mixing speed for 400r/min water-bath in react 2h after, at room temperature stand 1～2h, Ran Houfen
Product is not washed with ethanol and distilled water, 65 DEG C dry to constant weight.
4. weigh the pretreated stalk 5g of Jing (1) successively to steam in the 250mL triangular flasks of several different labels, plus 80mL
Distilled water infiltrates, and sequentially adds 5g Al2(SO4)3And 2.5mLDADMAC, stir and evenly mix, then add initiator ammonium ceric nitrate
0.833g, stirs.Logical nitrogen about 10min, and it is maintained at N2Under environment, it is 80 DEG C to be placed in bath temperature, and mixing speed is
In the water-bath of 400r/min, carry out respectively after reaction 1h, 2h, 3h, 4h and 5h, 1～2h is stood at room temperature, then use respectively
Ethanol and distilled water are washed to product, and 65 DEG C dry to constant weight.
5. weigh the pretreated stalk 5g of Jing (1) successively to steam in the 250mL triangular flasks of several different labels, plus 80mL
Distilled water infiltrates, and sequentially adds 5g Al2(SO4)3And 2.5mLDADMAC, stir and evenly mix, then add initiator ammonium ceric nitrate respectively
5g, 2.5g, 1.25g, 0.833g and 0.5g, stir.Logical nitrogen about 10min, and it is maintained at N2Under environment, water-bath temperature is placed in
Spend for 80 DEG C, then mixing speed uses respectively second in the water-bath of 400r/min, after reaction 2h, 1～2h to be stood at room temperature
Alcohol and distilled water are washed to product, and 65 DEG C dry to constant weight.
6. process test is carried out with the congo red waste water that 1.～modified straw for 5. producing is 50mg/L to concentration, is visited
Impact of each single factor test of rope to modified product absorption property, and find out major influence factors and carry out Orthogonal Optimization Test.Concrete examination
Test and the results are shown in Table 2～table 6.
The DADMAC dosage single factor test Treatment Analysis of table 2
The Al of table 32(SO4)3Dosage single factor test Treatment Analysis
The reaction temperature single factor test Treatment Analysis of table 4
5 reaction time of table single factor test Treatment Analysis
The initiator dosage single factor test Treatment Analysis of table 6
By to modifying agent DADMAC and Al2(SO4)3Dosage, reaction temperature, reaction time and initiator nitric acid
The single factor tests such as the dosage of cerium ammonium process test result analysis and understand, Al2(SO4)3Dosage, DADMAC dosages and reaction temperature
Three factors of degree are obtained material modified big to Congo red percent of decolourization luffing as variable changes in experimentation is prepared,
Affected more apparent by factor, so three kinds of factors are the principal element for affecting modified product absorption property.Tied by single factor experiment
Fruit simultaneously combines practical operation, and the suitable condition for selecting other non-principal factors is respectively：Reaction time is 2h, pretreated straw：
Ammonium ceric nitrate mass ratio (g/g) is 6：1, i.e., in this test ammonium ceric nitrate dosage is 0.833g, with Al2(SO4)3Dosage,
DADMAC dosages and reaction temperature carry out orthogonal test for principal element.Orthogonal test factor level table arranges such as table 7, orthogonal
Result of the test is shown in Table 8.
The orthogonal test factor level table of table 7
Table 8 be modified tabacco straw prepare orthogonal experiments
With reference to above single factor experiment and orthogonal experiments, the modified the best conditions of preparation pr ocess of optimization stalk is：
TS：DADMAC (g/mL) is 1：2, TS：Al2(SO4)3(g/g) it is 1：2,60 DEG C of reaction temperature, the reaction time is 2h, TS：Nitric acid
Cerium ammonium (g/g) is 6：1.
Modified straw is produced with stalk cellulose reaction using dimethyl diallyl ammonium chloride and aluminium salt, this is because two
Methyl diallyl ammonium chloride with good charge neutrality, is inhaled as a kind of nontoxic quaternary ammonium type organic cation monomer of cleaning
Attached, flocculation, purification, decolorization, contain thiazolinyl double bond in its molecular structure, can generate with other monomers or macromolecular copolymerization
Polymer substance.Simultaneously aluminium salt is also one of conventional raw material of water treatment agent, with good flocculation, decolorizing effect, certain bar
Also polymerisation can occur with other monomers or polymer substance under part.It is fine using organic and inorganic cationic monomer and stalk
The plain composite polymeric reaction of dimension, can introduce cation group and inorganic Al to cellulose long-chain, realize the inorganic-organic of stalk fibre
It is cation-modified.Additionally, in the stalk pretreatment stage, in order to improve stalk delignification ability, reinforcing fiber element activity, anti-
Answer and add in system certain density hydrogen peroxide (H2O2)。
2nd, modified straw is to dye wastewater treatment example
(1) congo red wastewater treatment
Congo red waste water is the dye wastewater that laboratory is prepared.Modified straw is in optimal modifying technology conditions
Under prepare.
1. impact of the modified straw dosage to Congo red removal effect.Take several 50mL triangular flasks and number, respectively
The modified straw of 0.002g, 0.005g, 0.010g, 0.020g, 0.030g, 0.050g and 0.100g is added, 25mL is subsequently adding
Concentration is the Congo red solution of 100mg/L.In being put into shaking table, at 20 DEG C of temperature (room temperature), with the rate oscillation of 150r/min
2h.Centrifugation, takes supernatant spectrophotometric determination absorbance, and then calculates Wastewater Dyes clearance and adsorbance
(being shown in Table 9).
The impact that the modified straw dosage of table 9 is removed to congo red
2. impact of the wastewater pH to Congo red removal effect.Take several 50mL triangular flasks and number, add 0.010g to change
Property stalk, be then respectively adding adjusted wastewater pH be followed successively by 3.00,5.00,7.00,9.00,11.00 100mg/L it is firm
Arnotto solution 25mL.In being put into shaking table, at a temperature of 20 DEG C, with the rate oscillation 2h of 150r/min.Centrifugation, takes supernatant
Spectrophotometric determination absorbance is used, and then calculates Wastewater Dyes clearance and adsorbance (being shown in Table 10).
The impact that the wastewater pH of table 10 is removed to congo red
3. impact of the reaction time of wastewater treatment to Congo red removal effect.Take several 50mL triangular flasks and number,
0.010g modified straws are added, the Congo red solution that 25mL concentration is 100mg/L is then respectively adding.In being put into shaking table, 20
At a temperature of DEG C, with the speed of 150r/min vibrate successively 2min, 5min, 10min, 20min, 30min, 1h, 1.5h, 2h, 3h,
4h, 8h, 12h, 24h, 36h and 48h.Centrifugation, takes supernatant spectrophotometric determination absorbance, and then calculates in waste water
Dyestuff clearance and adsorbance (being shown in Table 11), and using plan First order dynamic model [formula (1)] and intend second-order kinetics model [formula
(2)] result of the test is fitted (be shown in Table 12).
ln(qe-qt)=- k1t+lnqe (1)
In formula, k1To intend First order kinetic constant, min-1；k2To intend second-order kinetics constant, g. (mg.min)-1；qtFor
The instantaneous adsorbance of adsorption process, mg.g-1。
The impact that the reaction time of table 11 removes to congo red
The different dynamic equation of table 12 adsorbs Congo red fitting result to modified straw
4. modified straw is tested Congo red adsorption isotherm.Take several 50mL triangular flasks and number, add 0.010g
Modified straw, is then respectively adding 25mL concentration and is followed successively by 10mg/L, 20mg/L, 30mg/L, 50mg/L, 100mg/L, 150mg/
The Congo red solution of L, 200mg/L, 300mg/L, 500mg/L, 800mg/L, 1000mg/L.In being put into shaking table, in 20 DEG C of temperature
Under, with the rate oscillation 5h of 150r/min.Centrifugation, takes supernatant spectrophotometric determination absorbance, and then calculates useless
Dyestuff clearance and adsorbance (being shown in Table 13) in water, and using Langmuir Isothermal Models (formula (3)) and Freundlich isothermals
Model (formula (4)) is fitted (be shown in Table 14) to result of the test.
In formula, qmFor the maximal absorptive capacity (mg.g of adsorbent-1)；ceFor the equilibrium concentration (gm.L of solute in solution-1)；qe
Adsorbance (the mg.g of adsorbent during to balance-1)；klAnd kfRespectively Langmuir types, the coefficient of Freundlich type equations.
Congo red water treatment effect under the conditions of the different waste strengths of table 13
The different isothermal adsorpting equations of table 14 adsorb Congo red fitting result to modified straw
(2)P-PO4 3-Wastewater treatment
P-PO4 3-Waste water is the simulation phosphorus-containing wastewater that laboratory is prepared using potassium dihydrogen phosphate.Modified straw is most preferably to change
Prepare under property process conditions.
1. modified straw dosage is to P-PO4 3-The impact of removal effect.Take several 50mL triangular flasks and number, respectively
Add the modified straw of 0.002g, 0.005g, 0.010g, 0.015g, 0.020g, 0.030g, 0.050g, 0.100g and 0.200g
Stalk, is subsequently adding the phosphorus solution that 25mL concentration is 20mg/L.In being put into shaking table, at 20 DEG C of temperature (room temperature), with 150r/min
Rate oscillation 2h.Centrifugation, takes supernatant spectrophotometric determination absorbance, and then calculates P-PO in waste water4 3-Remove
Rate and adsorbance (being shown in Table 15).
The modified straw dosage of table 15 is to P-PO4 3-The impact of removal
2. wastewater pH is to P-PO4 3-The impact of removal effect.Take several 50mL triangular flasks and number, add 0.020g to change
Property stalk, is then respectively adding the P- that adjusted wastewater pH is followed successively by 3.00,5.00,7.00,9.00,11.00 20mg/L
PO4 3-Solution 25mL.In being put into shaking table, at a temperature of 20 DEG C, with the rate oscillation 2h of 150r/min.Centrifugation, takes supernatant
Spectrophotometric determination absorbance is used, and then calculates the clearance and adsorbance (being shown in Table 16) of Phosphorus From Wastewater.
The wastewater pH of table 16 is to P-PO4 3-The impact of removal
3. the reaction time of wastewater treatment is to P-PO4 3-The impact of removal effect.Take several 50mL triangular flasks and number,
0.020g modified straws are added, the phosphorus solution that 25mL concentration is 20mg/L is then respectively adding.In being put into shaking table, in 20 DEG C of temperature
Under, with the speed of 150r/min vibrate successively 2min, 5min, 10min, 20min, 30min, 1h, 1.5h, 2h, 3h, 4h, 8h,
12h, 24h, 36h and 48h.Centrifugation, takes supernatant spectrophotometric determination absorbance, and then calculates P-PO in waste water4 3-
Clearance and adsorbance (being shown in Table 17), and using plan First order dynamic model [formula (1)] and intend second-order kinetics model [formula (2)]
Result of the test is fitted (be shown in Table 18).
The reaction time of table 17 is to P-PO4 3-The impact of removal
The different dynamic equation of table 18 adsorbs P-PO to modified straw4 3-Fitting result
4. modified straw is to P-PO4 3-Adsorption isotherm test.Take several 50mL triangular flasks and number, add 0.020g
Modified straw, be then respectively adding 25mL concentration be followed successively by 1mg/L, 2mg/L, 5mg/L, 10mg/L, 20mg/L, 30mg/L,
The P-PO of 50mg/L, 100mg/L, 200mg/L, 400mg/L, 600mg/L, 1000mg/L4 3-Solution.In being put into shaking table, at 20 DEG C
At a temperature of, with the rate oscillation 30h of 150r/min.Centrifugation, takes supernatant spectrophotometric determination absorbance, Jin Erji
Calculate P-PO in waste water4 3-Clearance and adsorbance (being shown in Table 19), and using Langmuir Isothermal Models [formula (3)] and
Freundlich Isothermal Models [formula (4)] are fitted (be shown in Table 20) to result of the test.
P-PO under the conditions of the different waste strengths of table 194 3-Treatment effect
The different isothermal adsorpting equations of table 20 adsorb P-PO to modified straw4 3-Fitting result
(3) different disposal agent is to congo red waste water and P-PO4 3-The treatment effect contrast of waste water
1. 28 50mL conical flask with stopper are taken and number consecutively is 1-n, 2-n, 3-n, 4-n (n=1,2,3,4,5,6,7).
The modified tabacco straw of 0.005g, 0.010g, 0.020g, 0.030g, 0.050g, 0.080g, 0.100g is weighed respectively successively to 1-n
In number triangular flask；Weigh 0.005g, 0.010g, 0.020g, 0.030g, 0.050g, 0.080g, 0.100g tabacco straw respectively to arrive
In 2-n triangular flasks, 0.005g, 0.010g, 0.020g, 0.030g, 0.050g, 0.080g, 0.100g pretreatment is weighed respectively
Tabacco straw in 3-n triangular flasks, weigh respectively 0.005g, 0.010g, 0.020g, 0.030g, 0.050g, 0.080g,
0.100g activated carbons are in 4-n triangular flasks.Then 25ml concentration is all separately added into in all triangular flasks for the firm of 100mg/L
Annotto waste water (wastewater pH=6.48), is placed in shaking table, controls temperature for 20 DEG C, and velocity of vibration is 150r/min, at concussion
Reason 5h, the congo red waste water centrifugal after process is separated, supernatant spectrophotometric determination absorbance, and then calculates each
Clearance (be shown in Table 21) of the inorganic agent to congo red.
The different disposal agent of table 21 is compared congo red water treatment effect
2. 28 50mL conical flask with stopper are taken and number consecutively is a-n, b-n, c-n, d-n (n=1,2,3,4,5,6,7).
The modified tabacco straw of 0.005g, 0.010g, 0.020g, 0.030g, 0.050g, 0.080g, 0.100g is weighed respectively successively to a-n
In number triangular flask；Weigh 0.005g, 0.010g, 0.020g, 0.030g, 0.050g, 0.080g, 0.100g tabacco straw respectively to arrive
In b-n triangular flasks, 0.005g, 0.010g, 0.020g, 0.030g, 0.050g, 0.080g, 0.100g pretreatment is weighed respectively
Stalk weighs respectively 0.005g, 0.010g, 0.020g, 0.030g, 0.050g, 0.080g, 0.100g in c-n triangular flasks
Activated carbon (removing after phosphorus) is in d-n triangular flasks.Then 25ml concentration is all separately added into in all triangular flasks for 20mg/
The P-PO of L4 3-Waste water (wastewater pH=5.01), is placed in shaking table, controls temperature for 20 DEG C, and velocity of vibration is 150r/min, at concussion
Reason 30h, by process after containing P-PO4 3-Waste water centrifugal is separated, supernatant spectrophotometric determination absorbance, and then calculates each
Inorganic agent is to P-PO4 3-Clearance (being shown in Table 22).
The different disposal agent of table 22 is to P-PO4 3-Water treatment effect compares
From table 21 and table 22, by being modified to tabacco straw after for (Congo red to different anions waste water
Waste water from dyestuff and P-PO4 3-Waste water) purified treatment effect be significantly better than that its preparing raw material tabacco straw and pretreated cigarette
Careless stalk, and conventional activated carbon of sorbent.China is large agricultural country, and substantial amounts of agricultural stalk is produced every year, except little portion
Divide outside for compost, feed, remaining major part all carries out burning disposal, be not only not reaching to recycling, and burn product
Raw flue gas can bring a series of environment, social concern.By carrying out cation-modified process to stalk described in this experiment, no
Only can well solve the above problems, and for the process of anionic pollutant waste water has good effect, realize agriculture
Industry changing waste into resources is using the dual purpose with environmental improvement.
The modified straw of table 23 is constituted and specific surface area characterization result table with the element of tabacco straw
Claims (8)
- It is 1. a kind of to process the method containing anionic pollutant waste water using modified tabacco straw, it is characterised in that：The method is adopted The graft copolymerization of organic and inorganic cationic monomer carries out stalk fibre and is modified, and first tabacco straw is carried out with sodium hydroxide solution Stalk cellulose is isolated in pretreatment, then in N2Under environmental protection, with ammonium ceric nitrate as initiator, by pretreated tobacco Stalk and dimethyl diallyl ammonium chloride and aluminum sulfate carry out graft copolymerization, and it is material modified to prepare stalk, recycles this It is material modified respectively to the removal of organic anion pollutant and inorganic anion pollutant in water body, it is final to realize containing anion The process of pollutant waste water;Stalk is modified to be concretely comprised the following steps：Stalk 5g after pretreatment is weighed in 250mL triangular flasks, plus 80mL distills water infiltration, is subsequently adding Al2(SO4)3And dimethyl diallyl ammonium chloride, stir and evenly mix, add initiator nitre Sour cerium ammonium, stirs evenly;Logical nitrogen 10min, and it is maintained at N2Under environment, regulating and controlling temperature, reaction a period of time;1～2h is stored at room temperature, Priority ethanol and distilled water washes clean, 65 DEG C of drying, it is material modified to obtain final product tabacco straw, wherein, pretreated straw g:Two Methyl diallyl ammonium chloride mL is 1:4～4:1st, pretreated straw g：Al2(SO4)3G is 1:4～4:1st, reaction temperature is 20 ～100 DEG C, the reaction time be 1～5h, pretreated straw g：Ammonium ceric nitrate g is 1:1～10:1.
- 2. it is according to claim 1 to process the method containing anionic pollutant waste water, its feature using modified tabacco straw It is：Described employing organic and inorganic cationic monomer graft copolymerization carries out stalk fibre and is modified, and the modifying agent that it is adopted is for two Methyl diallyl ammonium chloride and aluminum sulfate, wherein dimethyl diallyl ammonium chloride are the aqueous solution of weight/mass percentage composition 60%.
- 3. the modified tabacco straw of utilization according to claim 1 or claim 2 is processed containing anionic pollutant waste water Method, it is characterised in that：Described pretreated straw and dimethyl diallyl ammonium chloride and Al2(SO4)3Respectively adding ratio Hybrid reaction is carried out for 1g/4mL and 1g/2g.
- 4. the modified tabacco straw of utilization according to claim 1 or claim 2 is processed containing anionic pollutant waste water Method, it is characterised in that：The pretreated straw is 6 with the mass ratio of ammonium ceric nitrate:1.
- 5. the modified tabacco straw of utilization according to claim 1 or claim 2 is processed containing anionic pollutant waste water Method, it is characterised in that：The weight/mass percentage composition of described NaOH is 10%.
- 6. the modified tabacco straw of utilization according to claim 1 or claim 2 is processed containing anionic pollutant waste water Method, it is characterised in that：Organic anion pollutant waste water be congo red simulated wastewater, inorganic anion pollutant waste water For the P-PO that potassium dihydrogen phosphate is prepared4 3-Simulated wastewater.
- 7. the modified tabacco straw of utilization according to claim 1 or claim 2 is processed containing anionic pollutant waste water Method, it is characterised in that：Waste water taken amount is 25mL when processing Pollutants in Wastewater using modified tabacco straw.
- 8. the modified tabacco straw of utilization according to claim 1 or claim 2 is processed containing anionic pollutant waste water Method, it is characterised in that：Concussion speed is 150r/min when processing Pollutants in Wastewater using modified tabacco straw, is controlled respectively Modified tabacco straw dosage is 0.002～0.200 g, wastewater pH is to be 2min～48h in 3～11, reaction time, wherein, just Annotto waste strength is 100mg/L, in terms of P, P-PO4 3-Simulated wastewater concentration is 20mg/L.
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